New polyurethanes and their use for the thickening of aqueous systems

ABSTRACT

The invention relates to a new hydrophilic/water-soluble or water-dispersible polyurethane comprising the reaction product of  
     A) at least one polyether polyol a1) having a average functionality of ≧3 and at least one urethane group-containing polyether polyol a2) having an average functionality of ≧4,  
     B) at least one monoalcohol with 6 to 22 carbon atoms,  
     C) at least one (cyclo)aliphatic and/or aromatic diisocyanate  
     D) optionally at least one monoisocyanate with 4 to 18 carbon atoms, and  
     E) optionally at least one polyisocyanate having a average functionality of &gt;2,  
     wherein the starting NCO/OH equivalent ratio is between 0.5:1 to 1.2:1, and which is suitable as thickening agents for aqueous systems, with a particularly efficient thickening effect in the high-shear range.

BACKGROUND OF THE INVENTION

[0001] The present invention relates to a hydrophilic/hydrophobicwater-soluble or water-dispersible polyurethanes suitable as thickeningagent for aqueous systems, having a particularly efficient thickeningeffect in the high-shear range, as well as its use for the thickening ofaqueous systems.

[0002] Polyurethane-based thickening agents for aqueous systems aredescribed in numerous publications, (see for example DE-A 1 444 243,DE-A 3 630 319, EP-A-0 031 777, EP-A-0 307 775, EP-A-0 495 373, U.S.Pat. Nos. 4,079,028, 4,155,892, 4,499,233 or 5,023,309).

[0003] A common feature of these thickening agents belonging to theprior art is the simultaneous presence of (i) hydrophilic segments in anamount of at least 50 wt. %, (ii) hydrophobic segments in an amount ofat most 10 wt. % and (iii) urethane groups. The term “hydrophilicsegments” is understood to mean in particular polyurethane chains withat least 5 chain members whose alkylene oxide units contain at least 60mole % of ethylene oxide units. The term “hydrophobic segments” isunderstood to mean in particular hydrocarbons segments with at least 6carbon atoms that are incorporated within the chain and/or arepreferably incorporated in the terminal position.

[0004] The thickening agents according to the invention describedhereinafter also preferably correspond to this definition.

[0005] These polyurethane thickening agents are suitable as auxiliarysubstances for adjusting the rheological properties of aqueous systems,such as automotive and industrial paints, plaster paints and coatingcompounds, printing inks and textile dyes, pigment printing pastes,pharmaceutical and cosmetic preparations, plant protection formulationsor filler dispersions.

[0006] Although the known polyurethane thickeners have a wideapplication, they are nevertheless insufficiently effective for someareas of application. A particular problem in the use of polyurethanethickeners is that they must exhibit a good effect not only in the rangeof low shear rates (which is important in particular for the settlingbehaviour and flow of for example paints), but also at high shear rates(high-shear range) that occur when applying the preparations using forexample brushes or rollers, or also by spraying. For these reasons inthe prior art two basic types of thickeners for the respective range ofthe shear rates are generally used in a preparation, or furtherauxiliary substances are added, such as solvents, in order to reduce thelow-shear viscosity. This often employed measure leads however to anincrease in volatile and/or migration-capable fractions in the paintformulation, which is undesirable in particular for environmentalprotection reasons.

[0007] In the past many attempts have been made in order to improve theeffectiveness of aqueous polyurethane thickeners, such as by theincorporation of hydrophobic segments in the polymer chain of thethickener or by the use of hydrophobic side chains. The increasingdemands in the market have led however over the last few years to theneed for even further improved products. By using thickening agents thatare improved compared to the prior art either paints with improvedcoating properties would be obtained using the same application amount,or alternatively the same coating properties could be achieved by usinga lower application amount, which would also lead to economic advantagescompared to the old systems.

[0008] It is an object of the invention to provide newpolyurethane-based thickening agents for aqueous or mainly aqueoussystems that have an improved effectiveness in the high-shear range.

[0009] This object was achieved by the hydrophilic/hydrophobicwater-soluble or water-dispersible polyurethanes according to theinvention which are described in more detail hereinafter. The essentialfeature of the invention is the specific incorporation of selectedhydrophilic and/or hydrophobic segments by using special alcohols and/orspecial alcohol mixtures, as well as the use of special polyethers asreaction partners for the isocyanate component.

SUMMARY OF THE INVENTION

[0010] The invention relates to a water-soluble or water-dispersiblepolyurethane containing a reaction product of

[0011] A) at least one polyether polyol a1) having an averagefunctionality of ≧3 and at least one urethane group-containing polyetherpolyol a2) having an averagefunctionality of ≧4,

[0012] B) at least one monoalcohol with 6 to 22 carbon atoms,

[0013] C) at least one (cyclo)aliphatic and/or aromatic diisocyanate

[0014] D) optionally at least one monoisocyanate with 4 to 18 carbonatoms, and

[0015] E) optionally at least one polyisocyanate having an averagefunctionality of >2,

[0016] wherein the starting NCO/OH equivalent ratio is between 0.5:1 to1.2:1.

[0017] The present invention also relates to a process for theproduction of this water-soluble or water-dispersible polyurethane byreacting

[0018] A) a mixture of at least one polyether polyol a1) having anaverage functionality of ≧3 and at least 1 urethane group-containingpolyether polyol a2) having an average functionality of ≧4,

[0019] B) at least one monoalcohol with 6 to 22 carbon atoms,

[0020] C) at least one (cyclo)aliphatic and/or aromatic diisocyanate,

[0021] D) optionally at least one monoisocyanate with 4 to 18 carbonatoms, and

[0022] E) optionally at least one polyisocyanate having an averagefunctionality of >2

[0023] at a starting NCO/OH equivalent ratio of 0.5:1 to 1.2:1.

[0024] The invention also relates to a process for adjusting the flowproperties of an aqueous paint system, adhesive and another aqueousformulation by adding this polyurethane to the aqueous paint system,adhesive and another aqueous formulation.

DETAILED DESCRIPTION OF THE INVENTION

[0025] Polyether polyol component A) contains a mixture of a polyetherpolyol a1) of formula (I)

R₁[—O—(A)_(x)—H]_(y)  (I),

[0026] wherein

[0027] R₁ represents an aliphatic or araliphatic hydrocarbon radicalwith 4 to 36 carbon atoms and optionally having ether oxygen atoms,

[0028] A represents ethylene oxide and/or propylene oxide radicals withthe proviso that at least 50 mole %, preferably 70 mole % andparticularly preferably 100 mole % of the radicals represent ethyleneoxide radicals,

[0029] x represents a number from 30 to 250, and

[0030] y represents a number from 3 to 18, preferably 3 to 6,

[0031] and a urethane group-containing polyether polyol a2) of formula(II)

[0032] wherein

[0033] R₁ represents an aliphatic or araliphatic hydrocarbon radicalwith 4 to 36 carbon atoms optionally containing ether oxygen atoms,

[0034] R₂ represents an aliphatic, araliphatic, cycloaliphatic oraromatic radical with 4 to 12 carbon atoms,

[0035] A represents ethylene oxide and/or propylene oxide radicals withthe proviso that at least 50 mole %, preferably at least 70 mole % andparticularly preferably 100 mole % of the radicals represent ethyleneoxide radicals,

[0036] x represents a number from 30 to 250,

[0037] y represents a number from 3 to 18, preferably 3 to 6, and

[0038] z represents a number from 2 to 16, preferably 2 or 4, andt=(y−z).

[0039] Monoalcohol component B) contains at least one monohydric alcoholof formula (III)

R₃—OH  (III),

[0040] wherein

[0041] R₃ represents an aliphatic, cycloaliphatic, aromatic oraraliphatic hydrocarbon radical with 6 to 22, preferably 6 to 18, morepreferably 8 to 14 carbon atoms and optionally having inertsubstituents, e.g. halogen.

[0042] Component C) contains at least one diisocyanate of formula (IV)

OCN—R₄—NCO  (IV),

[0043] wherein

[0044] R₄ represents an aliphatic, araliphatic, cycloaliphatic oraromatic radical with 4 to 22 carbon atoms and optionally containinginert substituents, e.g. halogen.

[0045] It is understood by the skilled artisan that the groups R₃ and R₄can optionally contain substituents that preferably are inert to theisocyanate group or the hydroxy group of the respective reactionpartner.

[0046] Component D) optionally contains at least one monoisocyanate offormula (V)

R₃—NCO  (V),

[0047] wherein

[0048] R₃ has the meaning given in formula (III).

[0049] Component E) contains at least one aliphatic, araliphatic,cycloaliphatic, heterocyclic or aromatic polyisocyanate with afunctionality of >2.

[0050] The production of polyether a1) on which the mixture of polyetheralcohols A) is based is carried out in a manner known per se byalkoxylation of corresponding polyhydric alcohols of the formula (VI)

R₁—[OH]_(y)  (VI),

[0051] wherein

[0052] R₁ and y have the meaning given for formula (I),

[0053] using ethylene oxide and optionally propylene oxide in a mixtureand/or arbitrary sequence. Suitable initiators include glycerol,trimethylolpropane, trimethylolethane, pentaerythritol,di-trimethylolpropane, sorbitol, sugars, etc. Glycerol,trimethylolpropane and sorbitol are preferably used, and glycerol andsorbitol are more preferably used.

[0054] The production of polyether alcohol mixture A) containingpolyethers a1) and urethane group-containing polyethers a2) is carriedout by the partial reaction of polyethers a1) with at least one organicisocyanate having a functionality of ≧2. In this context up to 50 mole%, preferably up to 20 mole % and more preferably up to 10 mole % ofpolyethers a1) may be reacted with isocyanates. The reaction is carriedout in a temperature range from 0° to 180° C., preferably 20° to 160° C.and more preferably 60° to 120° C.

[0055] Examples of monoalcohol components B) include aliphatic alcoholssuch as 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol,2-ethylhexanol, 1-nonanol, 1-decanol, 1-dodecanol, stearyl alcohol, etc.Monoalcohols with 6 to 16 carbon atoms are preferred, monoalcohols with8 to 14 carbon atoms being more preferred.

[0056] Examples of diisocyanates of component C) include aliphaticdiisocyanates such as 1,4-butane diisocyanate or 1,6-hexanediisocyanate; cycloaliphatic diisocyanates such as1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (isophoronediisocyanate), 1,3- and 1,4-cyclohexane diisocyanate,4,4′-diisocyanatodicyclohexylmethane, and others, as well as aromaticdiisocyanates such as 2,4-diisocyanatotoluene and4,4′-diisocyanatodiphenylmethane.

[0057] Examples of monoisocyanate component D) include aliphaticmonoisocyanates such as 1-butyl isocyanate, 1-pentyl isocyanate, 1-hexylisocyanate, 1-heptyl isocyanate, 1-octyl isocyanate, 1-nonyl isocyanate,1-decyl isocyanate, 1-dodecyl isocyanate, stearyl isocyanate, etc.Preferred are isocyanates with 8 to 18 carbon atoms, monoisocyanateswith 10 to 18 carbon atoms being more preferred.

[0058] Examples of polyisocyanate component E) include commerciallyavailable lacquer polyisocyanates, in other words in particular theknown modification products of simple diisocyanates containing urethanegroups, uretdione groups, allophanate groups and in particular biuretgroups, isocyanurate groups and iminooxadiazine-dione groups, examplesof suitable diisocyanates include 1,6-diisocyanatohexane,1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophoronediisocyanate), 4,4′-diisocyanatodicyclohexylmethane,1,4-diisocyanatocyclohexane, 1-methyl -2,4-diisocyanatocyclohexane andits mixtures with up to 35 wt. %, based on the total mixture, of1-methyl-2,6-diisocyanatocyclohexane; 2,4-diisocyanato-toluene and itsmixtures with up to 35 wt. %, referred to the total mixture of2,6-diisocyanototoluene or its mixtures. More preferably used are thecorresponding lacquer polyisocyanates with aliphatically and/orcycloaliphatically bound, free isocyanate groups. A suitablepolyisocyanate that does not contain the aforementioned groupings is4-isocyanatomethyl-1,8-octane diisocyanate.

[0059] Laquer polyisocyanates containing urethane groups include forexample the reaction products of 2,4- and optionally2,6-diisocyanatotoluene or 1-methyl-2,4-diisocyanatocyclohexane andoptionally 1-methyl-2,6-diisocyanatocyclohexane with sub-stoichiometricamounts of trimethylolpropane, or their mixtures with simple diols suchas the isomeric propanediols or butanediols. The production of suchurethane group-containing laquer polyisocyanates in practicallymonomer-free form is described for example in DE-A 1 090 196.

[0060] The biuret group-containing laquer polyisocyanates that are morepreferred for use according to the invention include in particular thosebased on 1,6-diisocyanatohexane and are described for example in EP-A 0003 505, DE-A 1 101 394, U.S. Pat. No. 3,358,010 or U.S. Pat. No.3,903,127.

[0061] The more preferred isocyanurate group-containing laquerpolyisocyanates include also in particular the trimers or mixed trimersof the diisocyanates mentioned above, such as the isocyanurategroup-containing polyisocyanurates based on diisocyanatotoluenedescribed in GB-A 1 060 430, GB-A 1 506 373 or GB-A 1 485 564, the mixedtrimers of diisocyanatotoluene with 1,6-diisocyanatohexane, which may beobtained for example according to DE-A 1 644 809 or DE-A 3 144 672, andin particular the aliphatic, aliphatic-cycloaliphatic and cycloaliphatictrimers or mixed trimers based on 1,6-diisocyanatohexane and/orisophorone diisocyanate, which may be obtained for example according toU.S. Pat. No. 4,324,879, U.S. Pat. No. 4,288,586, DE-A 3 100 262, DE-A 3100 263, DE-A 3 033 860 or DE-A 3 144 672. The laquer polyisocyanatesthat may be used according to the invention generally have an isocyanatecontent of 5 to 25 wt. %, a average NCO functionality of 2.1 to 5.0,preferably 2.8 to 4.0, and a residual content of starting monomericdiisocyanates of less than 2 wt. %, preferably less than 0.5 wt. %.Mixtures of the laquer polyisocyanates may also be used.

[0062] The production of the polyurethanes according to the invention iscarried out in one or several stages. A one-stage reaction in thiscontext means for example the reaction of the total amount of componenta1) with the total amount of components B), C), optionally D) andoptionally E). Component A) is then formed in situ depending on thechosen amount of component C). A multi-stage reaction means for examplereacting part of the component a1) with part of component C), followedby reacting resultant component A) with component B), the remainder ofcomponent C), as well as optionally components D) and E). A multi-stagereaction can also or additionally contain a separate reaction of part ofor the total amount of monoalcohol components B) with a molar excess ofdiisocyanate components C) followed by reaction of the resulting NCOprepolymer with the previously produced component A) and optionallycomponents D) and E). The sequence of the reactions is in this case notparticularly important, and it only has to be ensured that component A)according to the above definition can be formed by suitably choosing theamounts to be used of components A) to C) and optionally D) and E).

[0063] The polyurethanes according to the invention are generallycolorless to yellowish waxes or highly viscous polymers having softeningpoints or softening ranges within the temperature range from 10° to 80°C. For subsequent use it is often advantageous to mix the polyurethanesaccording to the invention with additives, such as formulation agents,solvents, water, emulsifiers or stabilizers, to form liquidformulations.

[0064] The polyurethanes according to the invention are suitable forthickening aqueous or predominantly aqueous systems. Example includeapplications in the field of colorants, leather treatment and paperauxiliary substances, preparations for petroleum extraction, detergentand adhesive preparations, waxes for polishes, formulations forpharmaceutical and veterinary purposes, plant protection preparations,cosmetics articles, etc. Also water itself can be thickened with thepolyurethane thickeners according to the invention so that optionallyfurther additives can be added or alternatively the water itself can beadded to aqueous preparations. The thickeners according to the inventionmay also be used in mixtures with other thickening agents, such as thosebased on polyacrylates, cellulose derivatives or inorganic thickeningagents.

[0065] Examples of aqueous systems that can be thickened according tothe invention also include aqueous polyacrylate dispersions, aqueousdispersions of copolymers of olefinically unsaturated monomers, aqueouspolyvinyl acetate dispersions, aqueous polyurethane dispersions, aqueouspolyesters dispersions and in particular ready-for-use preparations ofthe type already described above based on such dispersions or mixturesof such dispersions.

[0066] In one embodiment the thickening agents according to theinvention may used in bulk, preferably as granules or optionallypowders. It is preferred however to use liquid formulations that cancontain, in addition to the polyurethanes according to the invention,also water, solvents such as butyl diglycol, isopropanol, methoxypropylacetate, ethylene glycol and/or propylene glycol, non-ionic emulsifiers,surfactants and/or optionally further additives since in this way theincorporation of the thickening agents according to the invention intoaqueous or predominantly aqueous systems is substantially facilitated.

[0067] The ready-for-use preparations of the thickening agents accordingto the invention are particularly preferably aqueous solutions ordispersions having a solids content of 10 to 80, preferably 30 to 60 andparticularly preferably 40 to 50 wt. %.

[0068] The amount of thickening agents according to the invention thatis added to the aqueous or predominantly aqueous systems in order toachieve the desired thickening effect depends on the intended use andmay be determined by the person skilled in the art in a few preliminaryexperiments. As a rule 0.05 to 10 wt. %, preferably 0.1 to 4 wt. % andparticularly preferably 0.1 to 2 wt. % of the thickening agent accordingto the invention is used, these percentage figures referring to thesolids content of the thickening agent on the one hand and to the solidscontent of the aqueous system to be thickened on the other hand.

[0069] The evaluation of the effectiveness of the thickening agentsaccording to the invention may be carried out by known methods, forexample in a Haake rotary viscosimeter, in a Stormer or Brookfieldviscosimeter, or in an ICI viscosimeter.

EXAMPLES

[0070] Raw Materials Used

[0071] Polyether a₁): I Polyether based on glycerol and a mixture ofethylene oxide and propylene oxide (ratio 75:25) and with an OH numberof ca. 18 mg KOH/g II Polyether based on sorbitol and a mixture ofethylene oxide and propylene oxide (ratio 93.2:6.8) and an OH number ofca. 18 mg KOH/g

[0072] DBTL: Dibutyltin Dilaurate

[0073] Production of the Polyurethanes According to the Invention

Example 1

[0074] One-Pot Reaction

[0075] 915 g (0.3 mole OH groups) of polyether I were weighed out undernitrogen in a 2 I capacity glass flask and freed from traces of waterwithin 5 hours at 1 mbar/125° C. After cooling to 80° C., 14.26 g of1-octanol (0.11 mole OH groups) and 22.1 g of 1-decanol (0.14 mole OHgroups) were added and stirred for 15 minutes. 55.5 g of isophoronediisocyanate (0.50 mole isocyanate groups) and 0.09 g of DBTL were nextadded at 80° C. and then stirred at 80° C. until isocyanate bands couldno longer be detected by IR spectroscopy. A highly viscous, paleyellowish polyurethane resin was obtained.

Example 2

[0076] Two-Stage Process

[0077] 915 g (0.3 mole of OH groups) of polyether I were weighed outunder nitrogen in a 2 I capacity glass flask and freed within 5 hoursfrom traces of water at 1 mbar/125° C. After cooling to 120° C., 1.11 gof isophorone diisocyanate were added (0.01 mole of isocyanate groups)and stirred at 120° C. until isocyanate bands could no longer bedetected by IR spectroscopy. After cooling to 80° C., 14.26 g of1-octanol (0.11 mole of OH groups) and 22.1 g of 1-decanol (0.14 mole ofOH groups) were added and stirred for 15 minutes. Following this 54.39 gof isophorone diisocyanate (0.49 mole of isocyanate groups) and 0.09 gof DBTL were added at 80° C. and then stirred at 80° C. until isocyanatebands could no longer be detected by IR spectroscopy. A highly viscous,pale yellowish polyurethane resin was obtained.

[0078] The polyurethane thickeners listed in the following Table 1 wereproduced similarly to Example 1 and dissolved after completion of thereaction to form 60% solutions in water, Levalin FD (commercial productfrom Bayer AG) and Emulsifier WN (commercial product from Bayer AG)(ratio 3:2:1). In the case where monoisocyanates are used the polyetheremployed is first of all completely reacted with the monoisocyanate, andonly then is the reaction with the alcohols and the diisocyanate carriedout.

[0079] The polyurethane thickeners listed in the following Table 2 wereproduced similarly to Example 2 and after completion of the reactionwere dissolved to form 60% solutions in water, Levalin FD and EmulsifierWN (ratio 3:2:1).

[0080] The specified gram-equivalents do not represent thegram-equivalent amounts actually employed, but represent thegram-equivalent ratio of the reactants that are used. TABLE 1Polyurethane thickeners according to Example 1 Diiso- Polyether cyanateMonoisocyanate Monoalcohol Cata- Ex. # (g.-eq.) (g.-eq.) (g.-eq.)(g.-eq.) lyst 3 I (3.0) IPDI — 1-dodecanol (2.5) DBTL (5.0) 4 I (3.0)IPDI — 1-decanol (2.5) DBTL (5.0) 5 I (3.0) IPDI — 1-dodecanol (0.5)DBTL (5.0) 1-decanol (2.0) 6 I (3.0) IPDI — 1-decanol(1 .67) DBTL (5.0)2-ethylhexanol (0.83) 7 I (3.0) IPDI — 1-decanol (1.25) DBTL (5.0)1-octanol (1.25) 8 I (3.0) IPDI — 1-octanol (2.5) DBTL (5.0) 9 I (3.0)IPDI stearyl isocyanate 1-decanol (0.7) DBTL (2.5) (1.25) 1-octanol(0.55) 10 II (6.0) IPDI stearyl isocyanate 1-dodecanol (2.0) DBTL (3.5)(2.0) 11 II (6.0) IPDI dodecyl 1-octanol (1.0) DBTL (2.0) isocyanate(3.0) 12 II (6.0) IPDI dodecyl 1-decanol (1.0) DBTL (2.0) isocyanate(4.0) 13 II (6.0) IPDI dodecyl 1-dodecanol (2.0) DBTL (3.0) isocyanate(3.0)

[0081] TABLE 2 Polyurethane thickeners according to Example 2 PolyetherDiisocyanate Monoalcohol Ex. # (g.-eq.) (g.-eq. 1/ g.-eq. 2) (g.-eq.)Catalyst 14 I (2.9) IPDI (0.1/4.9) 1-decanol (1.4) DBTL 1-octanol (1.1)15 I (2.9) IPDI (0.3/5.0) 1-decanol (1.4) DBTL 1-octanol (1.1) 16 I(2.9) IPDI (0.1/5.25) 1-decanol (1.4) DBTL 1-octanol (1.1) 17 I (2.9)IPDI (0.3/5.25) 1-decanol (1.4) DBTL 1-octanol (1.1) 18 I (3.0) IPDI(0.1/5.0) 1-decanol (1.4) DBTL 1-octanol (1.1) 19 I (2.9) IPDI(0.5/5.15) 1-decanol (1.4) DBTL 1-octanol (1.1) 20 I (2.9) IPDI(0.65/5.0) 1-decanol (1.4) DBTL 1-octanol (1.1)

Comparison Example 1

[0082] 1) Production of a Prepolymer from Isophorone Diisocyanate and1-Dodecanol

[0083] 1110 g of isophorone diisocyanate (10 gram-equivalents) wereplaced under a nitrogen atmosphere in a 2 I capacity three-necked flaskequipped with stirrer, reflux cooler and dropping funnel and heated to100° C. while stirring. 186 g (1 gram-equivalent) of 1-dodecanol werethen added dropwise within 60 minutes. The mixture was then stirred fora further 2 hours at 100° C. Following this the resultant product wassubjected to thin layer distillation (170° C., 0.25 mbar) and the excessisophorone diisocyanate was thereby completely removed. A colorlessviscous resin with an isocyanate content of 10.8% was obtained.

[0084] 2. Production of a Polyurethane Thickener Using a Prepolymer

[0085] The procedure of Example 3 was followed except that the polyetherI was reacted with the aforedescribed prepolymer instead of withIPDI/dodecanol. A pale yellow resin was formed that was dissolved toform a 60% solution in water, Levalin FD® and Emulsifier WN® (3:2:1).

[0086] Examples of Use

[0087] The following examples show that emulsion paints having improvedbrushing properties (“brush resistance”) can be obtained with thethickening agents according to the invention.

[0088] Production of the coating compound and testing of the coatingproperties

[0089] The following constituents are dispersed over 30 minutes in a1000 ml flask with 100 glass beads (Ø 3 mm) using a Skandex disperser:AMP (aminopropanol)¹⁾ 1.25 g Borchigen ND (25% in H₂O)²⁾  6.8 g NeocrylAP 2860 (20%) defoaming agent³⁾  1.6 g Thickener (50%) 10.0 g TiO₂ RHD-2(Tioxide Company) 112.5 g  Methoxybutanol  8.5 g Propylene glycol  8.5 gButyl diglycol  8.5 g H₂O 22.35 g  then after the addition of H₂O 50.0 gNeocryl XK 62 (42%)⁴⁾ 270.0 g  500.0 g 

[0090] is dispersed for a further 30 minutes. The colorant is freed fromthe glass beads and after a maturation time of ca. 12 hours was coatedonto a plastics film (Linetta film) using a brush. The quality of thecoat (coating properties) are evaluated on a scale ranging from I (verygood) to X (very poor) (“brush resistance” in Tables 3 to 5).

[0091] The viscosity measurements were made in the low-shear range at10.3s⁻¹ using an Haake VT 500 viscosimeter (measurement body SV DIN),and in the high-shear range at 10000s⁻¹ using a Physika Rheolabviscosimeter. TABLE 3 Application technology testing of the products ofTable 1 Viscosity (mPa · s) at s⁻¹ Brushing Example No. 10.3 10000Properties  3 7300 170 IV-V 16500^(a)) 200 V  4 2500 280 III  5 3900 170V  6 1500 240 III  7 1600 260 III  8  400 160 III-IV  9 8500 200 IV 1028000  150 VI 11 5800 170 V 12 6300 190 IV 13 27600  160 VI Ascomparison: Bermodol 2110^(b))  450 110 VII Acrysol 2020^(c))  350 100VII Comp. Example 1 9200 130 VII

[0092] TABLE 4 Application technology testing of the products of Table 2Thickener from Viscosity (mPa · s) at s-1 Brushing Example No. 10.310000 Properties 14 950 220 III 15 1500 200 III 16 1500 300 III 17 1700300 III 18 900 240 III-IV 19 2100 260 III-IV 20 2500 280 III-IV Ascomparison: Bermodol 2110 450 110 VII Acrysol 2020 350 100 VII Comp.Example 1 9200 130 VII

[0093] Table 5 shows the use of the thickening agents according to theinvention in combination with cellulose derivatives (Walocel XM 20000PV; Borchers GmbH, Monheim) TABLE 5 Application technology testingProduct Ratio PUR Viscosity from Thickener/ Cellulose (mPa · s) at s⁻¹Brushing Example No. (wt. %, w.r.t. to paint) 10.3 10000 Properties 160.25:0.25 3100 120 VI 16 0.25:0.40 7100 150 V 16 0.80:0.40 7400 210 IV 6 0.50:0.40 8300 200 IV  7 0.50:0.40 7500 190 IV Comparison 0.50:0.407200 150 VI Bermodol 2110

[0094] Summary

[0095] From the test results given in Tables 3 to 5 it can clearly beseen that the polyurethane thickeners according to the invention have abetter thickening effect in the high-shear range and generally have abetter thickening effect in the low-shear range than the comparisonproducts. The brushing properties of the paints with the polyurethanethickeners according to the invention are in all cases better than thebrushing properties of the paints containing the comparison products.

[0096] Although the invention has been described in detail in theforegoing for the purpose of illustration, it is to be understood thatsuch detail is solely for that purpose and that variations can be madetherein by those skilled in the art without departing from the spiritand scope of the invention except as it may be limited by the claims.

What is claimed is:
 1. A water-soluble or water-dispersible polyurethane comprising the reaction product of A) at least one polyether polyol a1) having a average functionality of ≧3 and at least one urethane group-containing polyether polyol a2) having an average functionality of ≧4, B) at least one monoalcohol with 6 to 22 carbon atoms, C) at least one (cyclo)aliphatic and/or aromatic diisocyanate D) optionally at least one monoisocyanate with 4 to 18 carbon atoms, and E) optionally at least one polyisocyanate having an average functionality of >2, wherein the starting NCO/OH equivalent ratio is between 0.5:1 to 1.2:1.
 2. The polyurethane of claim 1 wherein polyether polyol a1) has an average functionality of 3 to
 4. 3. The polyurethane of claim 1 wherein polyether polyol a1) has an average functionality of 4 to
 6. 4. The polyurethane of claim 1 wherein monoalcohol B) has 6 to 18 carbon atoms.
 5. The polyurethane of claim 1 wherein diisocyanate C) is a (cyclo)aliphatic diisocyanate.
 6. The polyurethane of claim 1 wherein monoisocyanate D) has 8 to 18 carbon atoms.
 7. The polyurethane of claim 1 obtained in a one-stage or multi-stage reaction.
 8. The polyurethane of claim 1 wherein urethane group-containing polyether polyol a2) is produced by partial reaction of polyether polyol a1) with a diisocyanate.
 9. The polyurethane of claim 8 wherein urethane group-containing polyether polyol a2) is produced by partial reaction of polyether polyol a1) with a polyisocyanate having an average functionality of ≧2.
 10. A process for the production of the water-soluble or water-dispersible polyurethane of claim 1, comprising reacting A) a mixture of at least one polyether polyol a1) having an average functionality of ≧3 and at least 1 urethane group-containing polyether polyol a2) having an average functionality of ≧4, B) at least one monoalcohol with 6 to 22 carbon atoms, C) at least one (cyclo)aliphatic and/or aromatic diisocyanate, D) optionally at least one monoisocyanate with 4 to 18 carbon atoms, and E) optionally at least one polyisocyanate having an average functionality of >2 at a starting NCO/OH equivalent ratio of 0.5:1 to 1.2:1.
 11. A process for adjusting the flow properties of an aqueous paint system, adhesive and another aqueous formulation comprising adding the polyurethane of claim 1 to the aqueous paint system, adhesive and another aqueous formulation.
 12. An aqueous paint system, adhesive and another aqueous formulation comprising the polyurethane of claim
 1. 